An estimate of the equilibrium speciation of sulfur vapor over solid sulfur and implications for planetary atmospheres

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Abstract

Sulfur allotropes have been observed in planetary atmospheres and are believed to have been present in the ancient Earth atmosphere. The vapor pressures of sulfur allotropes, especially S2, S3, and S4, are poorly known at typical atmospheric temperatures, but have generally been assumed to be high enough to represent significant gas phase abundances in model calculations. Here I present estimates of the speciation of the equilibrium vapor pressure over solid sulfur, which would seem to imply that the vapor pressures of most allotropes are too low at typical atmospheric temperatures for gas phase formation reactions to be important. However, consideration of the kinetics of condensation shows that gas phase sulfur allotrope reactions can be important under certain conditions. The implications for the mechanism of sulfur isotope mass-independent fractionation on early Earth are discussed. Implications for the presence of sulfur allotropes in Venusian clouds, the distribution of S2 in the atmosphere of Jupiter following the comet Shoemaker-Levy 9 impacts, and the observation of S2 in volcanic plumes on Io are also presented.

Original languageEnglish (US)
Pages (from-to)269-279
Number of pages11
JournalJournal of Sulfur Chemistry
Volume29
Issue number3-4
DOIs
StatePublished - Jun 1 2008
Externally publishedYes

Fingerprint

Sulfur
Vapors
Vapor pressure
Atmospheric temperature
Gases
Sulfur Isotopes
Earth atmosphere
Fractionation
Condensation
Earth (planet)
Kinetics

Keywords

  • Atmospheric chemistry
  • Mass-independent fractionation
  • Planetary atmospheres
  • Sulfur allotropes
  • Vapor pressure

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "An estimate of the equilibrium speciation of sulfur vapor over solid sulfur and implications for planetary atmospheres",
abstract = "Sulfur allotropes have been observed in planetary atmospheres and are believed to have been present in the ancient Earth atmosphere. The vapor pressures of sulfur allotropes, especially S2, S3, and S4, are poorly known at typical atmospheric temperatures, but have generally been assumed to be high enough to represent significant gas phase abundances in model calculations. Here I present estimates of the speciation of the equilibrium vapor pressure over solid sulfur, which would seem to imply that the vapor pressures of most allotropes are too low at typical atmospheric temperatures for gas phase formation reactions to be important. However, consideration of the kinetics of condensation shows that gas phase sulfur allotrope reactions can be important under certain conditions. The implications for the mechanism of sulfur isotope mass-independent fractionation on early Earth are discussed. Implications for the presence of sulfur allotropes in Venusian clouds, the distribution of S2 in the atmosphere of Jupiter following the comet Shoemaker-Levy 9 impacts, and the observation of S2 in volcanic plumes on Io are also presented.",
keywords = "Atmospheric chemistry, Mass-independent fractionation, Planetary atmospheres, Sulfur allotropes, Vapor pressure",
author = "James Lyons",
year = "2008",
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pages = "269--279",
journal = "Journal of Sulfur Chemistry",
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TY - JOUR

T1 - An estimate of the equilibrium speciation of sulfur vapor over solid sulfur and implications for planetary atmospheres

AU - Lyons, James

PY - 2008/6/1

Y1 - 2008/6/1

N2 - Sulfur allotropes have been observed in planetary atmospheres and are believed to have been present in the ancient Earth atmosphere. The vapor pressures of sulfur allotropes, especially S2, S3, and S4, are poorly known at typical atmospheric temperatures, but have generally been assumed to be high enough to represent significant gas phase abundances in model calculations. Here I present estimates of the speciation of the equilibrium vapor pressure over solid sulfur, which would seem to imply that the vapor pressures of most allotropes are too low at typical atmospheric temperatures for gas phase formation reactions to be important. However, consideration of the kinetics of condensation shows that gas phase sulfur allotrope reactions can be important under certain conditions. The implications for the mechanism of sulfur isotope mass-independent fractionation on early Earth are discussed. Implications for the presence of sulfur allotropes in Venusian clouds, the distribution of S2 in the atmosphere of Jupiter following the comet Shoemaker-Levy 9 impacts, and the observation of S2 in volcanic plumes on Io are also presented.

AB - Sulfur allotropes have been observed in planetary atmospheres and are believed to have been present in the ancient Earth atmosphere. The vapor pressures of sulfur allotropes, especially S2, S3, and S4, are poorly known at typical atmospheric temperatures, but have generally been assumed to be high enough to represent significant gas phase abundances in model calculations. Here I present estimates of the speciation of the equilibrium vapor pressure over solid sulfur, which would seem to imply that the vapor pressures of most allotropes are too low at typical atmospheric temperatures for gas phase formation reactions to be important. However, consideration of the kinetics of condensation shows that gas phase sulfur allotrope reactions can be important under certain conditions. The implications for the mechanism of sulfur isotope mass-independent fractionation on early Earth are discussed. Implications for the presence of sulfur allotropes in Venusian clouds, the distribution of S2 in the atmosphere of Jupiter following the comet Shoemaker-Levy 9 impacts, and the observation of S2 in volcanic plumes on Io are also presented.

KW - Atmospheric chemistry

KW - Mass-independent fractionation

KW - Planetary atmospheres

KW - Sulfur allotropes

KW - Vapor pressure

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JF - Journal of Sulfur Chemistry

SN - 1741-5993

IS - 3-4

ER -